DD262864A5 - METHOD FOR THE PRODUCTION OF ALPHA, OMEGA-DISUBSTITUTED POLYMERS, THE POLYDISPERSITAET ANYTHERS THE THEORETICAL VALUE BY RADICAL POLYMERIZATION - Google Patents

Abstract

The invention relates to a process for preparing a, v-disubstituted polymers whose polydispersity arbitrarily approaches the theoretical value, by free-radical polymerization, homo- or copolymerization of free-radically polymerizable monomers using one or more initiators. According to the invention, the degree of polymerization is maintained at the desired level by continuously increasing the temperature. In the case of a given heat program, the process according to the invention makes it possible to increase the conversion without worsening the polydispersity.

Description

Field of application of the invention

The invention relates to a process for the preparation of polymers whose polydispersity arbitrarily approximates the theoretical polydispersity and which are substituted in α, ω-positions by functional groups by means of radical homopolymerization or copolymerization using one or more initiators.

Characteristic of the known state of the art

The disubstituted in α, ω positions by functional groups polymers are prepared according to the known methods such that the Poiymerisationslösung containing the monomer or monomers and the initiator and the solvent is polymerized at a certain temperature and for a certain period of time. In any case, the functionality of the resulting polymer is determined by the incorporated radical containing the functional group. When hydrogen peroxide is used as the initiator, such as according to the process described in U.S. Patent No. 3,338,861, the functionality exceeds the desired value of 2.0, which is due to the high reactivity of the hydrogen peroxide-forming hydroxyl radical at the temperature used (118 -12O ⁰ C) is caused. Another disadvantage of the method is the very high dispersity value: M _w -M _n = 2.5-3.5 where M _{n is} the number average and ~ M _{w is} the weight average molecular weight.

When 4,4-azo-bis (4-cyano-n-pentanol) (ACP) is used as the initiator, the functionality is less than 2.0, and the polydispersity reaches the desired value of 1.5-1.6, only if the turnover is low (28-30%) (Reed, S .: J. Pol. Sci., Part A1,92029-2038 [1971]).

Hitherto, the best known method of maintaining polydispersity at a constant level has been disclosed by British Patent No. 957,652. The essence of this method is that the amount of initiator decomposed in the course of polymerization is replaced by continuous dosing, but even so, one could only achieve an almost constant polydispersity value. A disadvantage of the method is that the decrease in monomer during the polymerization is not supplemented, although by means of the extension of the basic principle to the Monomierdosierung theoretically

On the one hand, however, the application of an increased excess of monomer substantially decreases the reactor capacity (polymer production per unit time in each reactor), and on the other hand, the cost-increasing effect of recovering a larger amount of unreacted monomer significantly increases the production cost. Another disadvantage of the method is the very high initiator consumption.

, In the case of radical polymerization, it is a very difficult task to ensure the required polydispersity. One cause of this is that in the course of the polymerization, the initiator concentration decreases and, as a result, the radical-producing process slows down; h., the initiation rate decreases gradually. The other reason is that the monomer concentration is decreasing.

The lower decrease in monomer concentration and the strong decrease in initiator concentration combine together to increase the degree of polymerization and polydispersity.

Object of the invention

With the method according to the invention, the polymerization base is kept at the value to be achieved by continuously increasing the temperature.

Through a given heat program, the conversion can be arbitrarily increased without deterioration of polydispersity. Compared to conventional methods, the initiator consumption is reduced.

To carry out the process already functioning plants can be used. It can be easily automated ._

Explanation of the essence of the invention

The invention has for its object to bring about by eliminating the disadvantages of the known solutions, a process that enables the production of such polymers having any degree of polymerization and their Polydisperistät approaches the theoretical value arbitrarily.

The invention is based on the recognition that the above-mentioned purpose can be achieved completely if, in the course of the polymerization, the desired degree of polymerization is kept practically constant by increasing the temperature according to a corresponding program.

Another reason of the invention is the recognition that the regulation of the degree of polymerization can be practically realized by the increase in temperature when the polymerization process is simulated by an analytical formula or a computer and then performed according to the heating program obtained by the simulation process. Accordingly, the invention is a process for producing α, ω-disubstituted polymers whose polydispersity arbitrarily approximates the theoretical value by radical polymerization of radically polymerizable monomers using one or more initiators. According to the process of the invention, the degree of polymerization is kept at the value to be achieved by continuously increasing the temperature.

According to an expedient manner of carrying out the process according to the invention, the degree of polymerization is controlled by continuously increasing the temperature so that the polymerization process is carried out according to a heat program determined by such a function, which describes the change in temperature over time by means of independent variables influencing the process. Such variables are conveniently the initiator and monomer concentration, the starting temperature; the heating time, the desired degree of polymerization and the desired polydispersity, as well as the arrhenius parameters of the decomposition rate constants of the initiators and of the chain growth and chain termination rate constants characteristic of the monomer.

According to another expedient embodiment of the method according to the invention, the degree of polymerization is controlled by the continuous increase in temperature such that the polymerization process is simulated by an analytical formula or with the aid of a computer and the effective polymerization process is carried out according to the heat program obtained by the simulation method.

The computer simulation is practically implemented so practical that the initial data, preferably the initiator and monomer concentration, the starting temperature, the heating time, the desired degree of polymerization and the desired Polydisperistät and the Arrheniusschen parameters of the decomposition rate constants of. Initiators and of the chain growth and chain termination rate constants characteristic of the monomer are entered into the computer, then through the continuous change of the polymerization temperature in the function of the polymerization time (expediently of the order of seconds) the change in the degree of polymerization is followed analytically or by computer the necessary for the compensation of the change in the degree of polymerization heat program is calculated.

In the case of deviation from the required degree of polymerization, the computer selects such temperature values by varying the temperature or the polymerization time, or sets these into the polymerization system, in which the degree of polymerization again assumes the required value. In this way, an amount of points consisting of discrete temperature-time value pairs is obtained, which is called the periodic heat program. By refining the distance between the individual points, d. H. the polymerization time associated with each temperature, the continuous heating program is obtained, characterized in that at each point of the program (at each temperature value) the degree of polymerisation is identical to that required. In this way, a heat program prepared by determining the degree of polymerization with iteration is obtained even before the start of the process, according to which the polymerization gives the product with the desired molecular weight and polydispersity.

For practical implementation of the heat program - as already indicated above - the Arrhenius equation (s) of the decomposition rate constant (n) (ki of the initiator (s) and the quotient (k ₂ / Vk <i) of chain growth are - (k ₂ ) and the chain termination rate constant (M, which characterize the monomer (s)). These relationships are readily determinable from the methods or data used in the

Books by Bagdasarian or Bamford (Bagdasarian, BS: Theory of Radical Polymerization, Akademiai Kiado, Budapest, 1961 [in Hungarian]; Bamford, CH: Comprehensive Chemical Kinetics V. 14a, Elsevier, (1976) are known the lower limit of polydispersity in the radical polymerization:

- if the chain termination occurs exclusively by recombination: P _w / P _n _ = 1_ + a / 2 = 1.5; Functionality = 2.0;

If the chain termination occurs exclusively by disproportionation: P _w / P _n = 1 + α = 2.0, functionality = 1.0 and

1 + JIL

k ₂ m

where m the monomer concentration, α the probability of chain growth,

r = vWi / k / the stationary concentration of the growing radical, W-) the rate of initiation, P _{w is} the weight average of the degree of polymerization and P _{n is} the number average of the degree of polymerization.

In certain systems, the chain termination is mixed, the theoretical value of polydispersity is between 1.5 and 2.0, and the same of functionality between 2.0 and 1.0, if there is no chain transfer to the monomer. This latter undesirably affects the above values (increases polydispersity and lowers functionality). It should be noted that the value of the polydispersity can be further reduced, if necessary, by certain methods (fractionation, selective release, precipitation), but the use of these methods unduly increases the production cost. In the process, the value of the poly-d ispersitä t at constant temperature is constantly increasing. The temperature should be increased in such a way that the quotient χ = l <4r / k ₂ m = V (2k- | f χ "Q / k ₂ m) assumes the value χ s const. At each time point, taking into account the Arrhenius relationships this condition will be brought to the following form:

woAE = 1/2 (E ₁ + E ₄ ) -E ₂ , and their value is between 37.5 and 25kJ for various monomers, m (t) is the monomer monomer concentration,

x (t) the instantaneous initiator concentration,

A ₁ , A ₂ and A _{4 are} the pre-exponential factors of the corresponding arrhenius equations, T (t) the heat program and

f is the radical utilization factor.

The "quality" of the choice of heat program applied to a given polymerization process, i.e., the performance of the process, can be controlled as follows:

based on (2), at time t = 0:

at the time t = t

The quality factor of the experimental regime can be formed from the relationships (3) and (4):

The closer the Q value is to 1, the better the heat program, or the program is still good enough if the Q value forms an element of the following open interval:

0.75 <Q <1.25 (6)

If in the process according to the invention hydrogen peroxide or a mixture of hydrogen peroxide and an azo initiator (eg.

ACP) or azo initiator is used to initiate the polymerization process, then, if the polymerization reaction is carried out according to a suitable heat program, a product having the requisite polydispersity and functionality can be ensured.

So z. In the preparation of polybutadiene diol, the number average molecular weight of the product M _n = 2500-4000. The polydispersity is 1.5-1.6, the functionality is nearly 2.0.

When using the method according to the invention can α, ω-disubstituted polymers whose polydispersity and functionality approach the theoretical values, z. From butadiene and other conjugated dienes, free radically polymerizable vinyl monomers, acrylic and methacrylic acid esters, and acrylic and methacrylonitrile.

When using the process, the backbone of the polymer formed from butadiene contains primarily monomer units incorporated in the 1,4-position, i. the content of 1,4-cis + 1,4-trans units is more than 80%.

The polymer thus prepared contains reactive end groups in α, ω positions - ζ. As in the case of polybutadiene diol (HTPBD) r-OH groups - which enable the polymer to further chemical reactions. For example, polyurethane may be prepared from polymer diones with tolylene diisocyanate and a crosslinking agent.

The manufacturing method according to the invention is distinguished by the following advantages:

1. Through a given heat program, the conversion can be arbitrarily increased, without deterioration of polydispersity

(Pw / Pn).

2. With the appropriate choice of the heating program and the initial concentrations, any degree of polymerization with any desired formulation can be achieved.

3. The process does not require an excess consumption of initiator in relation to what is necessary in the radical polymerization processes, or it allows the total consumption of the initiator (in contrast to the process disclosed in British Patent No. 957652).

4. The practical implementation of the heating program does not require additional equipment or additional consumption of materials (see above).

5. The procedure can be carried out in an already functioning technological plant. It can be easily automated, even in already functioning facilities.

The process according to the invention will be explained in more detail by means of the following examples, without limiting the protection claim.

embodiments example 1

In a 1 liter Parr autoclave, 160 g of HTPBD prepolymer was prepared according to the following recipe: in 400 ml of sec-butanol, 4.045 g (0.108 mol / l) of ACP and 10 ml of 67 wt% (0.227 mol / l) of H ₂ C ₂ solved. After liberation of oxygen, 290.35 g (6.188 mol / l) of butadiene were introduced. When filling, there was a pressure of 186 kPa in the reactor. The process was carried out according to the following heat program:

quality factor

1.0024 1.0043 1.0047 1.0035 1.0045 1.0087 1.0127 1.0152 1.0188 1.0176 1.0156 1.0006 1.0027 1.0002 1.0002 1.0002 1, 0002 1,0002 1,0001

1,0006 1,0003 1,0007 1,0001 1,0003 1,0003 1,0001 1,0006 1,0009

1,0007 1,0002 1,0004 1,0002 1,0008 1,0009 1,0007

1,0007 1,0009 1,0006 1,001

1,0007 1,001

1.001

1.0002

1,0005 -

Temperature ("C) Reaction time (min.) 70 0 70.8 17.3 71.6 21.8 74.8 34.3 76.2 38.5 77.8 42.6 79.8 46.8 82.4 51 85.6 55.1 89.0 59.3 91.4 63..5 92.8 67.6 93.4 71.8 93.6 77 93.8 82.5 94.0 97 94.2 112.5 94.4 127.6 94.8 157 95.0 171.1 95.2 185 95.4 198.8 95.6 212 95.8 225.1 96.0 237.6 96.2 250.1 96.4 262.3 96.6 274.1 96.8 286 97.0 297.5 97.2 308.3 97.4 319.5 97.6 330 97.8 340.5 98.0 350.6 98.2 360.8 98.4 370.6 98.6 380.1 98.8. 389.3 99.0 398.5 99.2 407.6 99.4 416.5 99.6 425 99.8 433.5 100.0 441.6 100.2 449.8 100.4 457.6 100.6 465.1 100.8 472.6

Temperature ( ⁰ C) Reaction time (min 101.0 480.1 101.2 487.3 101.4 494.5 101.6 501.3 101.8 508.1

Temperature ( ⁰ C) Reaction time (min.) 70 0 71.0 20.3 72.0 24.8 73.0 29.3 74.2 33.5 75.6 37.6 77.2 41.8 79.2 46 82.0 50.1 85.8 54.3 91.0 58.5 94.8 62.6 96.2 66.8 96..6 71 96.8 75.5

Quality Score 1,0003 1,0007 1,0003 1,0006

At the end of the process the pressure was 100OkPa. After blowing, 160 g of polybutadiene diol were obtained. M _n = 3500, functionality: M _w / M _n : 1.56.

Example 2

In a 1 liter Parr autoclave, 159.16 g of butadiene-styrene copolymer was prepared. In 400 ml of sec-butanol, 4.074 g (0.018 mol / l) of ACP and 10 ml of 55 mass% (0.223 mol / l) of H ₂ O _{2 were} dissolved. Thereafter, 83 ml (75.13 g) of styrene were added. After the liberation of oxygen, 226.6 g of butadiene were introduced. The copolymerization was carried out according to the following heat program:

Quality Score 1.0094 1.0048 1.0051 1.0047 1.0029 1.0019 1.0048 1.0093 1.0121 1.0238 1.0304 1.0170 1.0035 1.0007 1.0001

At the end of the process, the pressure was 580 kPa. The resulting polymer had the following properties: M _n = 3460, M _w / M _n = 1.60, functionality: 1.98. The molar ratio of the styrene in the copolymer was 10.5%, and 83% of the incorporated 89.5% butadiene had the 1,4-structure and only 17% had the 1,2-structure.

Example 3

In a 1 liter Parr autoclave, 120 g of butadiene-methyl acrylate copolymer was synthesized. In 400 ml of sec-butanol, 4.074 g (0.018 mol / l) of ACP and 10 ml of 55 mass% (0.223 mol / l) of H ₂ O _{2 were} dissolved. Thereafter, 47 ml of methyl acrylate were added. After the liberation of oxygen, 262.62 g of butadiene gas was introduced. The copolymerization was carried out according to the following heat program:

Quality Score 1.0004 1.0023 1.0027 1.0054 1.0002 1.0017 1.0040 1.0097 1.0091 1.0155 1.0216 1.0172 1.0054 1.0026 1.0008 1.0001 1 , 0002 1,0002 1,0002 1,0002 1,0002 1,0001 1,0000 1,0006

Temperature ( ⁰ C) Reaction time (min.) 70 0 70.8 19 71.6 23.5 72.6 27.6 73.8 32.1 75.0 36.3 76.4 40.5 78.0 44.6 80.2 48.8 82.8 53 86.0 57.1 89.4 61.3 91.8 65.5 93.0 69.6 93.4 74.1 93.6 78.3 93.8 83.5 94.0 97.3 94.2 112.8 94.4 128 94.6 142.8 9: 1.8 157.3 95.0 171.5 95.2 185.3

-6- 261864

Temperature ( ⁰ C) Reaction time (min 95.4 199.1 95.6 212.3 95.8 225.5 96.0 238 96.2 250.5 96.4 262.6 96.6 274.5 96.8 286.3 97.0 297.8 97.2 309.0 97.4 319.8 97.6 330.3 97.8 340.8 98.0 351 98.2 361.1 98.4 371 98.6 380.5 98.8 390 99.0 399.1 99.2 408 99.4 416.8 99.6 425.3 99.8 438.8 100 442 100.2 450.1 100.4 458 100.6 465.5 100.8 473.3 · 101 480.5 101.2 487.6 101.4 494.8 101.6 501.6 101.8 508.5

Quality Score 1,0003 1,0007 1,0001 1,0003 1,0003 1,0001 1,0006

1.0009

1,0009. 1.0007 1.0001 1.0003 1.0002 1.0007 1.0009 1.0006 1.0011 1.0011 1.0006 1.0008 1.0005 1.0008 1.0006 1.0011 1.0009 1, 0011 1,0013 1,0004 1,0002 1,0006, 1,0002 1,0005 1,0015

The product obtained had the following properties: M _n = 3800; M _w / M _n - 1.50; Functionality: 2.01.

Example 4

In a 1 liter Parr autoclave, 163.4 g of butadiene-acrylonitrile copolymer was prepared. In 400 ml of sec-butanol was dissolved 4.0412 g (0.018 mol / l) of ACP and 10 ml of 55 wt% (0.223 mol / l) of H ₂ O ₂ . Thereafter, 75 ml (60.88 g) of akroninitrile monomer was added. After the liberation of oxygen, 224 g of butadiene gas was introduced. The copolymerization was carried out according to the following heat program:

Quality Score 1.0099 1.0004 1.0023 1.0009 1.0048 1.0012 1.0075 1.0065 1.0140 1.0183 1.0292 1.0206 1.0086 1.0001 1.0007 1.0004 1 , 0009 1,0001 1,0010 1,0004 1,0006 1,0004 1,0008 1,0008 1,0003

Temperature ( ⁰ C) Reaction time (min.) 70 0 71.0 20 71.8 24.1 72.8 28.3 73.8 '32.5 75.2 36.6 76.6 40.8 78.6 45 81.0 49.1 84.6 53.3 89.6 57.5 94.2 61.6 96.2 65.8 96.8 70.3 97.0 76.1 97.2 86.6 97.4 97.5 97.6 108.3 97.8 , - 118.5 - 98.0 129 98.2 138.8 98.4 148.6 98.6 158.1 98.8 167.6 99.0 176.8

99.2 99.4 99.6 99.8

100.0 100.2 100.4 100.6 100.8 101.0 101.2 101.4 101.6 101.8

185.6

194.5

203

211.5

219.6

227.8

235.6

243.5

251

258.1

265.6

272.5

279.6

286.1

1,0005 1,0002 1,0006 1,0004 1,0008 1,0007 1,0012 1,0010 1,0001 1,0013 1,0003 1,0014 1,0002 1,0012

At the end of the process there was a pressure of 855 kPa. The resulting polymer had the following properties: M _n = 4000, M _w / M _n = 1/56, functionality: 2.03.

Example 5

In a 1 liter Parr reactor, 150 g of butadiene-methyl methacrylate copolymer were prepared. In 400 ml of sec-butanol was dissolved 4.037 g (0.018 mol / l) of ACP and 10 ml of 55 mass% (0.223 mol / l) of H ₂ O ₂ . To the initiator solution was added 80 ml (75 g) of methyl methacrylate, then the solution was deoxygenated and 225 g of butadiene were introduced. The polymerization was carried out according to the following heat program:

Temperature ( ⁰ C) Reaction time (min.) quality factor 70 0 1.0069 71.0 20 1.0019 71.8 24.5 1.0035 72.8 28.6 1.0017 73.8 32.8 1.0050 75.0   37 1.0072 76.6 41.1 1,004t 73.4 45.3 1.0070 80.6 49.5 1.0138 83.6 53.6 1.0192 87.6 57.8 1.0214 91.4 62 1.0204 93.6 66.1 1.0113 94.6 70.3 1.0013 95.0 70.3 1.0113 95.2 83.3 1.0004 95.4 96.8 1.0001 95.6. 110 1.0005 95.8 123.1 1.0000 96.0 135.6 1.0001 96.2 148.1 1.0001 96.4 160.3 1.0008 96.6 "172.5 1.0004 96.8 184 • 1,0007 97.0 195.5 1.0007 97.2 206.6 1.0005 97.4 217.5 1.0000 97.6 228 1.0002 97.8 238.5 1.0000 98.0 248.6 • 1,0005 98.2 258.8 1.0007 98.4 268.6 1.0005 98.6 278.1 1.0009 98.8 287.6 1.0009 99.2 305.6 1.0006 99.4 314.5 1.0003 99.6 323 1.0007 99.8 331.5 1.0005 100 339.5 1.0009 100.2 347.8 1.0008 100.4 355.6 1.001 100.6 363.5 1.0011 100.8 371 1.0002 101.0 378.1 1.0000

-8- ZÖZ öb4

Temperature ( ⁰ C) Reaction time (min.) 101.2 385.3 101.4 392.5 101.6 399.3 101.8 406.1

Quality Score 1.0004 1.0000 1.0003 1.0013

The pressure at the end of the process was 930 kPa. The properties of the obtained polymer were as follows: M _n = 3700; M _w / M _n = 1.65; Functionality: 1.93.

Example 6

In a 1 liter Parr autoclave, 90 g of polystyrene diol homopolymer was prepared. In 660 ml of benzene, 3.326 g (0.015 mol / l) of ACP and 14.96 ml of 80 wt.% (0.5 mol / l) of H ₂ O _{2 were} dissolved, then 183 g of styrene were added. The polymerization was carried out according to the following heat program:

Quality Score 1,0528 1,0500 1,0505 1,0511 1,0506 1,0507 1,0511 1,0501 1,0512 1,0517 1,0510 1,0512 1,0502 1,0501 1,0510 1,0505 1 , 0508 1,0521 1,0517 1,0523 1,0521 1,0508 1,0505 1,0527 1,0529 1,0518 1,0542 1,0542 1,0560 1,0559 1,0525 1,0548 1,0547 1,0603 1,0610 1,0621 1,0562 1,0592 1,0552 1,0509 1,0512 1,0517 1,0501 1,0502 1,0501 1,0500 1,0503 1,0501 1,0502 1, 0502

The polymer obtained had the following properties: M _n = 10590; M _w / M "= 1.59; Functionality: 1.96.

Temperature ( ⁰ C) Reaction time (min.) 60 0 60.4 27.6 60.6 33.5 60.8 38 61.2 46.6 61.4 50.8 61.6 55 62.0 59.1 62.2 64.6 62.6 68.8 63.0 74.3 63.4 79.5 63.8 84.6 64.2 89.5 64.6 94.3 65.0 99.1 65.4 103 65.8 108.1 66.2 112.6 66.6 116.8 67.2 121 67.8 125.8 68.4 130.3 69.0 134.8 69.6 139.3 70.4 143.5 71.2 152.5 72.0 152.5 73.0 156.6 74.0 161.1 75.2 165.3 76.4 1,169.5 77.8 173.6 79.2 177.8 80.8 182 82.4 186.1 84.0 190.3 85.2 194.5 86.2 198.6 87.0 202.8 87.4 207.3 87.8 211.5 88.0 217.3 88.2 223.8 88.4 247.6 88.6 276.5 88.8 304.6 89.0 332.5 89.2 359.3 89.4 385.8

-9- 26Z864

Example 7

In a 1 l Parr autoclave, 104 g of polybutadiene diol homopolymer were prepared, in 400 ml of sec-Buianol, 4.302 g (0.020 mol / l) of ACP and 8.9 ml of 76.2% by mass of H ₂ Q (0.238 mol / l). l) solved. After the liberation of oxygen, 260.5 g of butadiene gas was introduced. The polymerization was carried out according to the following heat program:

Quality factor 0.7524 0.7507 0.7515 0.7543 0.7513 0.7537 0.7526 0.7567 0.7611 0.7636 0.7708 0..7682 0.7565 0.751

0.75

0.7505 0.7506 0.7505 0.7501 0.7502 0.75

0.7503 0.7504 0.75

0, -7501 0.7508 0.7502 0.75

0.7504 0.7502 0.7506 0.7505 0.7509 0.7507 0.751

0.7507 0.7509 0.7505

The resulting polymer had the following properties: M _n = 4000; M _w / M _n = 2.33; Functionality: 2.07. The increased polydispersity proves that a significant deviation of the quality factor of 1.00 results in the increase of the quotient M _w / M _n .

Examples

In a 1 liter Parr autoclave, 127 g polybutadienediols were synthesized. In 400 ml of sec-butanol were dissolved 397 g (0.018 mol / l) of ACP and 8.9 ml of 75 mass% H ₂ O (0.248 mol / l). After the liberation of oxygen, 280 g of butadiene gas was introduced. The polymerization was carried out according to the following heat program:

Quality Score 1.2732 1.2502 1.2517 1.2561 1.2587 1.2515 1.2547 1.2601 1.2654 1.2653 1.2601 1.2537 1.255 1.2542

Temperature ( ⁰ C) Reaction time (min.) 70 0 70.8 10 71.6 14.1 72.6 18.3 73.8 22.8 75.0 27 76.6 31.1 78.4 35.3 80.8 39.5 84.4 43.6 89.6 47.8 94.4 52 96.4 56.1 97.0 60.3 97.2 64.8 97.4 71.6 97.6 82.5 97.8 93 98.0 103.1 98.2 113 98.4 122.8 98.6 132.3 98.8 141.8 99.0 151 99.2 159.8 99.4 168.6 99.6 177.5 99.8 185.6 100.0 193.8 100.2 202 100.4 2C9,8 100.6 217.6 100.8 225.1 101.0 232.6 101.2 239.8 101.4 247 101.6 253.8 101.8 260.6

Temperature ("C) Reaction time (min.) 70 0 71.2 21.6 72.0 25.8 73.0 30 74.2 34.5 75.6 39 77.0 43.1 78.6 47.3 80.6 51.5 85.2 59.8 87.4 64 89.0 68.1 90.0 72.3 90.6 76.8

-ΊΟ- 4.ΌΔ.

Temperature (° C) 90.8 91.0 91.2 91.4 91.6 91.8 92.0 92.2 92.4 92.6 92.8 93.0 93.2 93.4 93.6 93.8 94.0 94.2 94.4 94.6 94.8 95.0 95.2 95.4 95.6 95.8 96.0 96.2 96.4 96.6 96.8 97 0 97.2 97.4 97.6 S7.8 98.0 98.2 98.4 98.6 98.8 99.0 99.2 99.4 99.6 99.8 100 100.2 100.4 100.6 100.8 101.0 101.2 101.4 101.6 101.8

Reaction time (min.)

86.1

97.3 118.5 139.3 159.5 179.3 198.5 217.6 236.1 254.3 271.8 289.3 306.1 322.6 339.1 355 370.5 385.6 400 , 5 415 429.1 443

456.5 470 482.8 495.6 508.1 520.3 532.1 • 543.6 555.1 566.3 577.1 588 598.5 608.6 618.5 628.3 637.8 647, 3,656.5,665.3 674.1 683 691.1 699.3 707.5 715.3 723.1 730.6 738.1 745.3 752.5 759.3 766.1

Quality Score 1.2503 1.2502 1.2503 1.2506 1.2504 1.2504 1.25

1.2505 1.2505 1.2506 1.2501 1.2505 1.2502 1.25

1,2508 1,2507 1,2507 1,2507 1,2507 1,2506 1,2506 1,2504 1,2501 1,2508 1,2503 1,2506 1,2508 1,2508 1,2506 1,25

1.2504 1.2505 1.2502 1.2508 1.251

1.2508 1.2501 1.2503 1.25

1.2506 1.2506 1.25

1.2503 1.2514 1.2503 1.21

1.2506 1.2504 1.251

1.2508 1.2515 1.2511 1.2517 1.2512 1.2516 1.2508

The polymer obtained had the following properties: M _n = 3700; M _w / M _n = 2.02; Functionality: 2.06.

Significant deviation of polydispersity from theoretical value proves undesirable impact of increase in quality factor.

Claims (6)

A process for producing α, ω-disubstituted polymers whose polydispersity arbitrarily approximates the theoretical value by radical polymerization of radically polymerizable monomers using one or more initiators. Characterized in that the degree of polymerization is controlled by the continuous increase in temperature on the polymer value to be achieved. 2. The method of claim 1 for controlling the degree of polymerization by continuously increasing the temperature, characterized in that the polymerization process is carried out according to a heat program determined by such a function, which describes the change in temperature over time by means of independent variables influencing the processes. 3. The method according to claim 2, characterized in that the initiator and monomer concentration, the starting temperature, the heating time, the desired degree of polymerization and the desired polydispersity and the arrheniusschen parameters of the decomposition rate constants of the initiators and of the monomer characteristic chains of growth and chain termination rate constants are used as the process variable independent variables. 4. The method of claim 1 for controlling the degree of polymerization by continuously increasing the temperature, characterized in that the polymerization process is simulated by an analytical formula or with the aid of a computer and the effective polymerization process is carried out after the heat program obtained by the simulation method. 5. The method according to claim 4 for the practical realization of the computer simulation, characterized in that the output data are entered into the computer, then tracked by the continuous change in the polymerization in the function of the polymerization time, the change in the degree of polymerization by computer and for the compensation of Change in the degree of polymerization necessary heat program is calculated. 6. The method according to claim 5, characterized in that the initiator and monomer concentration, the starting temperature, the heating time, the desired degree of polymerization and the desired polydispersity and the Arrheniusschen parameters of the decomposition rate constants of the initiators and of the monomers characteristic chain growth and chain termination rate constants as the output information is entered into the computer.